CN105585017B - The industrialized preparing process of high-purity silicon dioxide - Google Patents
The industrialized preparing process of high-purity silicon dioxide Download PDFInfo
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- CN105585017B CN105585017B CN201610131771.3A CN201610131771A CN105585017B CN 105585017 B CN105585017 B CN 105585017B CN 201610131771 A CN201610131771 A CN 201610131771A CN 105585017 B CN105585017 B CN 105585017B
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
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Abstract
The present invention proposes a kind of industrialized preparing process of high-purity silicon dioxide, comprises the following steps：1) using industrial fluosilicic acid as raw material, reacted and distilled in distillation tower reactor with oxidant, obtain sterling fluosilicic acid；2) using industrial liquid ammonia as raw material, it is obtained into sterling gas ammonia by treating column；3) the sterling gas ammonia for obtaining the sterling fluosilicic acid that step 1) obtains with step 2) reacts in aminating reaction kettle, generation obtains silica solid and ammonium fluoride solution, and silica solid is separated by solid-liquid separating equipment to obtain silica crude product；4) the silica crude product that step 3) obtains is washed successively, pickling, washing and calcining, obtain high-purity silicon dioxide.The silica purity that this method is prepared can reach more than 99.9999%, and being capable of large-scale production.
Description
Technical field
The invention belongs to silica preparing technical field, and in particular to using industrial fluosilicic acid and industrial liquid ammonia as raw material system
The industrialized preparing process of standby high-purity silicon dioxide.
Background technology
The physicochemical property of high-purity silicon dioxide：Silica, molecular formula SiO2, molecular weight 60.08, relative density
2.319~2.635,1750 DEG C of fusing point.It is not soluble in water；Insoluble in acid, but hydrofluoric acid and hot concentrated phosphoric acid are dissolved in, bases and can be melted
Work.Two kinds of crystalline silica and amorphous silica are there are in nature.Silica have many uses it is general, mainly
For glass processed, waterglass, pottery, enamel, refractory material, aerogel blanket, ferrosilicon, molding sand, elemental silicon, cement etc..Titanium dioxide
Silicon is free of the crystallization water, is not involved in being filled the chemical reaction of thing, is a kind of highly stable neutral inorganic mineral filler.
Glass sand generally refers to SiO2Content is higher than 99.9% quartz (micro mist)；Ultra-pure quartz sand refers to SiO2
Content is higher than 99.99% quartz micropowder, and its low-end product dioxide-containing silica is 99.99~99.999% (4N~5N), high
End product SiO2 contents are higher than 99.9999% (>=6N).
So far, the preparation method of ultra-pure quartz sand is two kinds of techniques of Physical and chemical method.Physical is to use
Mineral crystal or high-purity natural quartz are raw material, and ultra-pure quartz is prepared through processes such as crushing, flotation, acid treatment, high-temperature process
Sand.Ultra-pure quartz sand is prepared using Physical, although handling process is extremely important, the natural quartz or crystal of high-purity,
It is the key for determining Physical success or not.At present, China lacks the natural quartz or crystal material of high-purity.
Chemical synthesis is that the silica product of high-purity is obtained by way of chemical reaction, then high-purity titanium dioxide
Quartz products are made in silicon；The technique of chemical synthesis high-purity silicon dioxide is simultaneously few, and one kind is to use organochlorosilane pyrohydrolysis
High-purity gas-phase silica (i.e. silica) is generated, then gas-phase silica melted to obtain high purity quartz；The main of this method lacks
Point is that removing chloride difficulty is larger, production cost is higher.Another kind is hydrolyzed using high-purity esters of silicon acis, and it is white to prepare high-purity precipitation
Carbon black, high-purity white carbon melting is then prepared into ultra-pure quartz；The reaction of the technique needs the processes such as acid catalysis, alkali precipitation,
Metal ion removal difficulty is larger, and quality is extremely difficult to 5N, and cost is higher.
It is also one of method of chemical synthesis high-purity silicon dioxide to prepare high-purity silicon dioxide with fluosilicic acid and liquefied ammonia reaction.
This method can prepare the very high product of purity in theory, but because technical problem is more, no one finds a conjunction always before this
The process route of reason.
The content of the invention
To solve the problems, such as silica that the reaction of existing fluosilicic acid and liquefied ammonia prepares to go out high-purity, present invention proposition one
The industrialized preparing process of kind high-purity silicon dioxide, the silica purity that this method is prepared can reach
More than 99.9999%, and being capable of large-scale production.
The technical proposal of the invention is realized in this way：
A kind of industrialized preparing process of high-purity silicon dioxide, comprises the following steps：
1) using industrial fluosilicic acid as raw material, reacted and distilled in distillation tower reactor with oxidant, obtain sterling fluorine silicon
Acid；
2) using industrial liquid ammonia as raw material, it is obtained into sterling gas ammonia by treating column；
3) the sterling gas ammonia for obtaining the sterling fluosilicic acid that step 1) obtains with step 2) reacts in aminating reaction kettle, obtains
To silica solid and ammonium fluoride solution, silica solid is separated by solid-liquid separating equipment to obtain silica
Crude product；
4) the silica crude product that step 3) obtains is washed successively, pickling, washing and calcining, obtain high-purity two
Silica.
Further, the water-washing method of the step 4) is to carry out reverse-flow flushing using pure water.
Further, the electrical conductivity of the pure water of the step 4) is 0.055~0.1 μ s/cm.
Further, acid used in the pickling of the step 4) is electron level acid, and the electron level acid is selected from sulfuric acid, hydrochloric acid, hydrogen
One or more in fluoric acid, phosphoric acid and fluosilicic acid.
Further, in the step 3) aminating reaction temperature be 55 DEG C~115 DEG C, reaction pressure be 0.06MPa~
0.35MPa。
Further, the calcining heat of the step 4) is 350 DEG C~850 DEG C.
Further, the oxidant of the step 1) is potassium permanganate or hydrogen peroxide.
Beneficial effects of the present invention
The silica purity that the method for the present invention is prepared can reach more than 99.9999%, and being capable of scale
Production.
Embodiment
Embodiment 1
1) using industrial fluosilicic acid as raw material, reacted and distilled in distillation tower reactor with potassium permanganate, in fluosilicic acid
Metal ion is changed into sediment, is evaporated after fluosilicic acid heating, is sterling fluosilicic acid in overhead condensation, bottom of towe sediment is periodically arranged
To Sewage Disposal；
2) using industrial liquid ammonia as raw material, its treating column by having been loaded with pure water by pure water, obtains in tower top
Sterling gas ammonia, pure water continuously enters tower, and continuously discharges waste water decontamination water treatment station；
3) the sterling gas ammonia for obtaining the sterling fluosilicic acid that step 1) obtains with step 2) reacts in aminating reaction kettle, instead
It is 110 DEG C~115 DEG C to answer temperature, and pressure is 0.20MPa~0.25MPa in kettle, and question response carries out separation of solid and liquid, obtained afterwards completely
Silica crude product and ammonium fluoride solution；
4) the silica crude product that step 3) obtains is carried out successively carrying out reverse-flow cleaning 6 times with pure water to remove dioxy
Ammonium fluoride above SiClx crude product, cleaning dope mixes with the ammonium fluoride solution that step 3) obtains, then by silica crude product
The electron level mixed acid formed with sulfuric acid and hydrochloric acid carries out pickling, and the silica after pickling is carried out into reverse-flow cleaning with pure water
7 times, the silica of wash clean is put into calcining in-furnace temperature and is fired to dry product for 700 DEG C~750 DEG C after aqueous is separated,
It is finished product (i.e. high-purity silicon dioxide) after cooling.
Wherein, the electrical conductivity of pure water is 0.055~0.1 μ s/cm.
Embodiment 2
1) using industrial fluosilicic acid as raw material, reacted and distilled in distillation tower reactor with hydrogen peroxide, in fluosilicic acid
Metal ion is changed into sediment, is evaporated after fluosilicic acid heating, is sterling fluosilicic acid in overhead condensation, bottom of towe sediment is periodically arranged
To Sewage Disposal；
2) using industrial liquid ammonia as raw material, its treating column by having been loaded with pure water by pure water, obtains in tower top
Sterling gas ammonia, pure water continuously enters tower, and continuously discharges waste water decontamination water treatment station；
3) the sterling gas ammonia for obtaining the sterling fluosilicic acid that step 1) obtains with step 2) reacts in aminating reaction kettle, instead
It is 100 DEG C~105 DEG C to answer temperature, and pressure is 0.30MPa~0.35MPa in kettle, and question response carries out separation of solid and liquid, obtained afterwards completely
Silica crude product and ammonium fluoride solution；
4) the silica crude product that step 3) obtains is carried out successively carrying out reverse-flow cleaning 4 times with pure water to remove dioxy
Ammonium fluoride above SiClx crude product, cleaning dope mixes with the ammonium fluoride solution that step 3) obtains, then by silica crude product
The electron level mixed acid formed with sulfuric acid and hydrochloric acid carries out pickling, and the silica after pickling is carried out into reverse-flow cleaning with pure water
4 times, the silica of wash clean is put into calcining in-furnace temperature and is fired to dry product for 350 DEG C~450 DEG C after aqueous is separated,
It is finished product after cooling.
Embodiment 3
1) using industrial fluosilicic acid as raw material, reacted and distilled in distillation tower reactor with potassium permanganate, in fluosilicic acid
Metal ion is changed into sediment, is evaporated after fluosilicic acid heating, is sterling fluosilicic acid in overhead condensation, bottom of towe sediment is periodically arranged
To Sewage Disposal；
2) using industrial liquid ammonia as raw material, its treating column by having been loaded with pure water by pure water, obtains in tower top
Sterling gas ammonia, pure water continuously enters tower, and continuously discharges waste water decontamination water treatment station；
3) the sterling gas ammonia for obtaining the sterling fluosilicic acid that step 1) obtains with step 2) reacts in aminating reaction kettle, instead
It is 55 DEG C~90 DEG C to answer temperature, and pressure is 0.06MPa~0.11MPa in kettle, and question response carries out separation of solid and liquid, obtains two afterwards completely
Silica crude product and ammonium fluoride solution；
4) the silica crude product that step 3) obtains is carried out successively carrying out reverse-flow cleaning 8 times with pure water to remove dioxy
Ammonium fluoride above SiClx crude product, cleaning dope mixes with the ammonium fluoride solution that step 3) obtains, then by silica crude product
The electron level mixed acid formed with sulfuric acid and hydrochloric acid carries out pickling, and the silica after pickling is carried out into reverse-flow cleaning with pure water
10 times, the silica of wash clean is put into calcining in-furnace temperature and is fired to dry product for 800 DEG C~850 DEG C after aqueous is separated,
It is finished product after cooling.
Embodiment 4
Embodiment 1-3 is prepared into finished product to determine using ICP method, the results are shown in Table 1：
The embodiment 1-3 high-purity silicon dioxide Quality Index Analysis results of table 1
| Sequence number | Detection project | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| 1 | SiO2 | W/% | 99.9999 | 99.9998 | 99.9999 |
| 2 | Al | ppm | 0.19 | 0.46 | 0.23 |
| 3 | B | ppm | 0.04 | 0.04 | 0.05 |
| 4 | Ca | ppm | 0.05 | 0.4 | 0.06 |
| 5 | Cr | ppm | 0.05 | 0.05 | 0.05 |
| 6 | Cu | ppm | 0.04 | 0.05 | 0.02 |
| 7 | Fe | ppm | 0.05 | 0.08 | 0.06 |
| 8 | K | ppm | 0.08 | 0.11 | 0.09 |
| 9 | Li | ppm | 0.05 | 0.12 | 0.06 |
| 10 | Mg | ppm | 0.05 | 0.06 | 0.05 |
| 11 | Mn | ppm | 0.03 | 0.05 | 0.03 |
| 12 | Na | ppm | 0.25 | 0.45 | 0.11 |
| 13 | Ni | ppm | 0.05 | 0.05 | 0.04 |
| 14 | Impurity adds up to | ppm | 0.93 | 1.92 | 0.85 |
Note：SiO is removed in detection project2Outer is impurity.
From table 1 it follows that high-purity silicon dioxide preparation technology route provided by the invention is feasible, its dioxy
SiClx purity equal more than 99.999%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (6)
1. a kind of industrialized preparing process of high-purity silicon dioxide, it is characterised in that comprise the following steps：
1) using industrial fluosilicic acid as raw material, reacted and distilled in distillation tower reactor with oxidant, obtain sterling fluosilicic acid；
2) using industrial liquid ammonia as raw material, it is obtained into sterling gas ammonia by treating column；
3) the sterling gas ammonia for obtaining the sterling fluosilicic acid that step 1) obtains with step 2) reacts in aminating reaction kettle, obtains two
Silica solids and ammonium fluoride solution, silica solid by solid-liquid separating equipment is separated to obtain silica thick
Product；
4) the silica crude product that step 3) obtains is washed successively, pickling, washing and calcining, obtain high-purity titanium dioxide
Silicon；
Wherein, the temperature of aminating reaction is 55 DEG C~115 DEG C in the step 3), and reaction pressure is 0.06MPa~0.35MPa,
The calcining heat of the step 4) is 350 DEG C~850 DEG C.
2. the industrialized preparing process of high-purity silicon dioxide according to claim 1, it is characterised in that the step 4)
Water-washing method be that reverse-flow flushing is carried out using pure water.
3. the industrialized preparing process of high-purity silicon dioxide according to claim 2, it is characterised in that the step 4)
The electrical conductivity of pure water be 0.055~0.1 μ s/cm.
4. the industrialized preparing process of high-purity silicon dioxide according to claim 1, it is characterised in that the step 4)
Pickling used in acid for electron level acid, the one kind of the electron level acid in sulfuric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid and fluosilicic acid
It is or a variety of.
5. the industrialized preparing process of the high-purity silicon dioxide according to any one of Claims 1-4, it is characterised in that
The oxidant of the step 1) is potassium permanganate or hydrogen peroxide.
6. the industrialized preparing process of high-purity silicon dioxide according to claim 1, it is characterised in that the step 1)
Oxidant be potassium permanganate or hydrogen peroxide.
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| CN108675310A (en) * | 2018-07-24 | 2018-10-19 | 衢州市鼎盛化工科技有限公司 | The method for preparing ultrapure quartz sand as raw material using fluosilicic acid |
| CN112310357B (en) * | 2019-07-29 | 2022-02-11 | 宁德时代新能源科技股份有限公司 | Silicon-oxygen compound and secondary battery containing same |
| CN111470767B (en) * | 2020-05-08 | 2022-07-05 | 江苏永鼎光纤科技有限公司 | Method for recycling and reusing solid waste quartz powder in tube outside deposition process |
| CN112194145A (en) * | 2020-09-23 | 2021-01-08 | 广西大学 | Industrial production and preparation method of ultra-high purity silicon dioxide powder material |
| CN112573525A (en) * | 2020-12-29 | 2021-03-30 | 无锡恒诚硅业有限公司 | High-purity silicon dioxide and preparation method and application thereof |
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| CN101028930A (en) * | 2006-03-01 | 2007-09-05 | 多氟多化工股份有限公司 | Method for linked producing ammonium fluoride and white carbon black |
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| CN103073040A (en) * | 2013-01-30 | 2013-05-01 | 昆明道尔森科技有限公司 | producing method of calcium fluoride with white carbon black |
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| CN101028930A (en) * | 2006-03-01 | 2007-09-05 | 多氟多化工股份有限公司 | Method for linked producing ammonium fluoride and white carbon black |
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